JP2011128589A - Colored photosensitive resin composition, pattern forming method, method for manufacturing color filter, color filter, and display device provided with the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition and a pattern forming method which is excellent in developability and can be restrained the occurrence of surface reticulation after post baking, and to provide a method for manufacturing a color filter having a colored pattern free from surface reticulation, and is excellent in line width sensitivity, linearity and heat resistance, and to provide the color filter and a display device. <P>SOLUTION: The colored photosensitive resin composition contains a colorant, a binder resin, a polymerizable compound, a photopolymerization initiator and a solvent, wherein the content of the colorant is 15-60 mass% by mass fraction based on the solid content of the colored photosensitive resin composition. The binder resin has a structure unit selected from a structure unit having an allyl group, a structure unit having an N-substituted maleimide group, and a structure unit having a cyclic imide group, and a structure unit having an acid group, in the molecule. The polymerizable compound is a carboxyl group-containing polyfunctional monomer, and the photopolymerization initiator is a lophine-based photopolymerization initiator or an oxime-based photopolymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition, a pattern forming method, a color filter manufacturing method, a color filter, and a display device including the same.

  As a method for producing a color filter, a method of applying a photolithography method using a colored photosensitive resin composition containing a colorant (such as an organic pigment), a binder resin, a polymerizable compound, and a photopolymerization initiator is known. ing. In order to obtain a higher-definition color filter, the colored photosensitive resin composition is excellent in developability and pattern formability, and the film formed using the colored photosensitive resin composition is heat resistant and smooth. It is required to have excellent properties.

  As the above colored photosensitive resin composition, various materials have been proposed from the viewpoint of the components to be contained. For example, for the purpose of reducing residues after development, a colored photosensitive resin composition characterized by the content of the colorant and the type of the polymerizable compound has been developed (for example, see Patent Document 1).

  As another proposal, an exposure processing means used in the photolithography method is specified, and a highly sensitive colored photosensitive resin composition is proposed for the exposure processing means. For example, a colored resin composition for exposure processing using excimer laser light has been developed (see, for example, Patent Document 2).

JP 2007-328148 A WO2008 / 084853

  As display devices such as liquid crystal displays are developed for television applications, further enhancement of color filters is desired, and the developability of the colored photosensitive resin composition and the colored photosensitive resin composition are used. Therefore, the smoothness of the formed film is required at a higher level. However, in the colored photosensitive resin composition and the method for producing a color filter using the same disclosed in Patent Documents 1 and 2 above, it is difficult to say that developability is sufficient, and surface reticulation (reticulated wrinkles). ) Was difficult to suppress.

In view of the above, it is an object of the present invention to provide a colored photosensitive resin composition having good developability and capable of suppressing the occurrence of surface reticulation after post-baking, and a pattern forming method using the same. To do.
Further, the present invention is obtained by a method for producing a color filter having a colored pattern in which occurrence of surface reticulation is suppressed and having excellent line width sensitivity, linearity, and heat resistance, and the method for producing the color filter. Another object is to provide a color filter and a display device including the color filter.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by the following method.

<1> At least (A) a colorant, (B) a binder resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and the content of the (A) colorant Is 15% by mass to 60% by mass with respect to the solid content of the colored photosensitive resin composition, and (B) the binder resin is in the molecule, (B-1) in the following general formula (I) (B-2) at least one selected from the group consisting of a structural unit having an N-substituted maleimide group, and (B-3) a structural unit represented by the following general formula (II) And (C) at least one of the polymerizable compounds is a carboxyl group-containing polyfunctional monomer, and (D) at least one of the photopolymerization initiators. Coloring where one type is a lophine photopolymerization initiator or an oxime photopolymerization initiator An optical resin composition.

In the general formula ^(I), the R 11 ^{to R 15} each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl ^{group, R 16} represents a hydrogen atom or a methyl group.

In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkylene group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. R ²³ and R ²⁴ may be bonded to each other to form a carbocycle.

<2> The colored photosensitive resin composition according to <1>, wherein the oxime photopolymerization initiator is a ketoxime photopolymerization initiator represented by the following general formula (III).

  In general formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of Xs are present, the plurality of Xs each independently represent a monovalent substituent and may be the same or different.

<3> The colored photosensitive resin composition according to <1> or <2>, wherein the carboxyl group-containing polyfunctional monomer has an acid value of 80 mgKOH / g to 200 mgKOH / g.
<4> The colored photosensitivity according to any one of <1> to <3>, further comprising (F) a sensitizer, wherein at least one of the sensitizers (F) is a monofunctional thiol compound. It is a resin composition.

<5> A colored layer forming step of coating the colored photosensitive resin composition according to any one of <1> to <4> on a substrate to form a colored layer, and a pattern-like pattern with respect to the colored layer The pattern formation method includes an exposure step of forming a latent image by exposing with an ultraviolet laser, and a development step of developing the colored layer on which the latent image is formed to form a pattern.
<6> The pattern forming method according to <5>, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.
<7> The pattern forming method according to <5> or <6>, wherein the ultraviolet laser is a pulse laser oscillated at a frequency of 20 Hz to 2000 Hz.

<8> A color filter manufacturing method including a step of forming a pattern on a substrate by the pattern forming method according to any one of <5> to <7>.
<9> A color filter manufactured by the manufacturing method according to <8>.
<10> A display device comprising the color filter according to <9>.

According to the present invention, it is possible to provide a colored photosensitive resin composition having good developability and capable of suppressing the occurrence of surface reticulation after post-baking, and a pattern forming method using the same.
Further, according to the present invention, by the method for producing a color filter having a colored pattern in which occurrence of surface reticulation is suppressed and having excellent line width sensitivity, linearity, and heat resistance, and the method for producing the color filter, The obtained color filter and a display device including the color filter can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
≪Colored photosensitive resin composition≫
The colored photosensitive resin composition of the present invention contains at least (A) a colorant, (B) a binder resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, (A) Content of a coloring agent is 15 mass%-60 mass% by mass fraction with respect to solid content of a coloring photosensitive resin composition, The said (B) binder resin is in a molecule | numerator, (B-1 A structural unit represented by the following general formula (I), (B-2) a structural unit having an N-substituted maleimide group, and (B-3) a structural unit represented by the following general formula (II). At least one structural unit selected from the group and a structural unit having an acidic group, wherein at least one of the polymerizable compounds (C) is a carboxyl group-containing polyfunctional monomer, D) At least one photopolymerization initiator is a lophine photopolymerization initiator or oxime Characterized in that it is a photopolymerization initiator.
Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described in detail.

<(A) Colorant>
The colored photosensitive resin composition of the present invention contains (A) at least one kind of colorant.
The content of the (A) colorant in the colored photosensitive resin composition of the present invention is 15% by mass to 60% by mass with respect to the solid content of the colored photosensitive resin composition. (A) When the content of the colorant is less than 15% by mass, it is necessary to set the film thickness thick in order to obtain a desired hue, which makes it difficult to develop or increases the tact time. Problems arise. On the other hand, when the content of the colorant (A) exceeds 60% by mass, the development time becomes long, and the profile shape becomes an inverted edge shape, which is not preferable.
The content of the colorant (A) in the colored photosensitive resin composition of the present invention is more preferably 20% by mass to 50% by mass, and further preferably 25% by mass to 40% by mass.

  As the colorant (A), a dye and a pigment can be appropriately selected and used. From the viewpoint of heat resistance and the like, a pigment is more preferable.

(A) The pigment used as the colorant may be an inorganic pigment or an organic pigment, but from the viewpoint of high transmittance, it is preferable to use a pigment having a particle size as small as possible. The average primary particle diameter is preferably 0.01 μm to 0.1 μm, more preferably 0.01 μm to 0.05 μm.
In the colored photosensitive resin composition of the present invention, by using the polymer dispersant described later, the pigment dispersibility and dispersion stability are improved even when the pigment size is small. Even if it is thin, a colored pixel having excellent color purity can be formed.

  Furthermore, in the present invention, among the pigments contained in the colored photosensitive resin composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and the primary The proportion of the pigment having a particle diameter exceeding 0.08 μm is preferably less than 5% in the total amount of the pigment.

When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, the heat resistance and chromaticity change can be prevented, and the ratio of the pigment having a primary particle diameter exceeding 0.08 μm is 5 When it is less than%, the contrast is good, the time-dependent stability of the colored photosensitive resin composition is good, and further, foreign matter failure can be prevented.
The proportion of the pigment having a primary particle size of less than 0.02 μm is more preferably less than 5% from the viewpoints of heat resistance and chromaticity change prevention.
The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 3% from the viewpoint of improving contrast.

  The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. For example, the particle size distribution can be grasped by measuring the total number of particles in the observation sample at 3 to 100,000 times and the number of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at 3 to 100,000 times, photographed, the major axis of 1000 primary particles is measured, less than 0.02 μm, and more than 0.08 μm Calculate the percentage of primary particles. This operation is performed for a total of three locations by changing the location of the pigment powder, and the results are averaged.

  (A) Examples of inorganic pigments that can be used as a colorant include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium And metal oxides such as magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

  C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 4, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37.

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a pigment for the red phase (R), an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment A pigment or a mixture of a perylene red pigment, an anthraquinone red pigment, a condensed dis red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and condensed condensed red pigments include C.I. I. Pigment red 242, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of red pigment to other pigment (red pigment: other pigment) is preferably 100: 5 to 100: 80. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

In addition, as a pigment for the green phase (G), a halogenated phthalocyanine pigment alone or a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment. Can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the pigment for the blue phase (B), a phthalocyanine pigment can be used alone or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  In the present invention, it is particularly preferable to use an organic pigment as a colorant and to coat the pigment with a polymer compound in the pigment miniaturization step or dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles It is more preferable to use a coating pigment excellent in dispersion stability in which primary particles are stably maintained.

  The coated pigment, which is a preferred embodiment in the present invention, is a pigment coated with a polymer compound. However, the coating is a new surface of a pigment having high surface activity generated by miniaturization. Since a strong coating layer of the polymer compound is formed by a strong electrostatic action, it is considered that a coated pigment having higher dispersion stability can be obtained. That is, in the present invention, the coated polymer compound is hardly released even when the pigment after coating treatment is washed with an organic solvent that dissolves the polymer compound.

  The coated pigment as used in the present invention is one in which pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocyclic ring in the side chain, and the polymer compound is a part of the pigment particle surface or By being firmly coated all over, a higher dispersion stability effect can be obtained, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The release amount (release rate) is calculated by washing the coated pigment with 1-methoxy-2-propanol. That is, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol, shaken at room temperature for 3 hours using a shaker, and then the pigment was allowed to settle for 8 hours at 80,000 rpm with a centrifuge. The mass of the solid content of the supernatant is determined by a drying method. The liberation rate (%) is calculated from the ratio between the mass of the solid content and the mass of the polymer compound used for the coating of the pigment.

The said free amount (free rate) about commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. Thus, it is calculated as “mass of the polymer compound used for the coating treatment of the pigment”. Separately, the pigment was washed with 1-methoxy-2-propanol, and the obtained liberation amount was divided by the “mass of the polymer compound used for the pigment coating treatment” to obtain the liberation rate (%). Ask for.
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coating treatment is preferably performed at the same time in the pigment refinement step. Specifically, (i) a pigment, (ii) a water-soluble inorganic salt, and (iii) a small amount that does not substantially dissolve (ii). (Iv) a step of adding a polymer compound and mechanically kneading with a kneader or the like to obtain a mixture (referred to as a salt milling step), throwing the mixture into water, a high speed mixer, etc. It is carried out through a step of stirring to form a slurry, and a step of filtering, washing with water and drying if necessary.

  The salt milling described above will be described more specifically. First, a small amount of (iii) a water-soluble organic solvent is added as a wetting agent to a mixture of (i) an organic pigment and (ii) a water-soluble inorganic salt, and after kneading strongly with a kneader or the like, the mixture is submerged in water. The mixture is stirred and stirred with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. In addition, when using it disperse | distributing to an oil-based varnish, it is also possible to disperse | distribute the process pigment (it is called a filter cake) before drying to an oil-based varnish, removing water by the method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

By using (iv) at least a partly soluble resin in combination with the above (iii) organic solvent during salt milling, the surface is further finely coated with (iv) at least a partly soluble resin. A pigment with little aggregation is obtained.
In addition, (iv) The timing which adds a high molecular compound may add all at the initial stage of a salt milling process, and may divide and add. It is also possible to add in the dispersion step.

  The polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment. In particular, those coated with a polymer compound having a heterocyclic ring in the side chain are preferred. Examples of such a polymer compound are disclosed in paragraph numbers [0029] to [0030] of JP-A-2008-83089 and paragraph numbers [0044] to [0047] of JP-A-2009-62457. Things can be used.

Even in the case of using the above-described coated pigment, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be further improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, polymer dispersants such as Disperse Aid 9100 (both manufactured by San Nopco);

Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.); F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, Asahi Denka Co., Ltd. and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 161, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (bit Chemie Co., Ltd.) and the like. In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

  The pigment derivative is one of polymer compounds used for coating the pigment, and is added to the pigment dispersion composition as necessary. The pigment is introduced into the photosensitive resin composition as fine particles by adsorbing a pigment derivative having a portion having affinity for the dispersant or a polar group to the pigment surface and using it as an adsorption point of the dispersant. The re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11. -199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, etc. can be used.

  As content in the pigment dispersion composition of a pigment derivative, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The dispersion method can be performed, for example, by finely dispersing a pigment and a dispersant previously mixed with a homogenizer or the like using a bead disperser using zirconia beads or the like. .

In the present invention, when a dye is used as the (A) colorant, a uniformly dissolved colored photosensitive resin composition is obtained.
(A) There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

<(B) Binder resin>
The colored photosensitive resin composition of the present invention contains (B) at least one binder resin.
(B) The binder resin contains (B-1) a structural unit represented by the following general formula (I), (B-2) a structural unit having an N-substituted maleimide group, and (B-3) in the molecule. ) It has at least one structural unit selected from the group consisting of structural units represented by the following general formula (II) and a structural unit having an acidic group.

[Structural unit of (B-1)]
The structural unit of (B-1) is represented by the following general formula (I).

In the general formula ^(I), the R 11 ^{to R 15} each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl ^{group, R 16} represents a hydrogen atom or a methyl group.

R ^{11 to} R ¹⁵ in the general formula (I) are each independently preferably a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 14 carbon atoms. An atom, a bromine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 7 carbon atoms, or an aryl group having 5 to 10 carbon atoms is more preferable.
The alkyl group may have a substituent, and the substituent may be linear, branched, or cyclic, and includes a methyl group, an n-propyl group, an iso-propyl group, a t-butyl group, and the like. An alkyl group having 1 to 7 carbon atoms is preferable. The aryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 7 carbon atoms or an aryl group having 5 to 14 carbon atoms, preferably a phenyl group, a furyl group, Naphthyl group.

Of these, preferred as the general formula (I) are those in which R ^{11 to} R ¹⁵ are each independently a hydrogen atom, a methyl group, a phenyl group or a halogen atom, and R ¹⁶ is a hydrogen atom or a methyl group.

[Structural unit of (B-2)]
(B-2) Examples of the structural unit having an N-position-substituted maleimide group include the structural units shown below.

[Structural unit of (B-3)]
The structural unit (B-3) is represented by the following general formula (II).

In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkylene group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. R ²³ and R ²⁴ may be bonded to each other to form a carbocycle.

Preferred as the general formula (II) is one in which R ²¹ is a hydrogen atom, R ²² is a methylene group or an ethylene group, and R ²³ and R ²⁴ are bonded to each other to form a 6-membered ring.

(B) The binder resin contains, in the molecule, (B-1) a structural unit represented by the general formula (I), (B-2) a structural unit having an N-position-substituted maleimide group, and (B-3) It suffices to have at least one structural unit selected from the group consisting of the structural units represented by formula (II), but it may have two or more.
(B) Binder resin is one of (B-1), (B-2), and (B-3), from the viewpoint of suppressing the occurrence of surface reticulation (network wrinkles). It is preferable to have.

  (B) The binder resin contains, in the molecule, (B-1) a structural unit represented by the general formula (I), (B-2) a structural unit containing an N-substituted maleimide group, and (B-3) It is preferable to have a total of 50 mol% to 90 mol% of structural units represented by the general formula (II), more preferably 50 mol% to 80 mol%, more preferably 60 mol% to 80 mol% It is. Within this range, film loss during development after exposure is reduced, and surface smoothness and development latitude are good.

[Structural unit having acidic group]
Furthermore, (B) binder resin has a structural unit which has an acidic group in a molecule | numerator.
Examples of the structural unit having an acidic group include a structural unit derived from a carboxyl group-containing unsaturated monomer. Examples of the carboxyl group-containing unsaturated monomer include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and other unsaturated monocarboxylic acids; maleic acid, maleic anhydride, fumaric acid, itaconic acid, Unsaturated dicarboxylic acid such as itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; trivalent or higher unsaturated polycarboxylic acid or the anhydride thereof; succinic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]; ω-carboxypolycaprolactone mono These are mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as (meth) acrylate.
Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
The carboxyl group-containing unsaturated monomers may be used alone or in combination of two or more.

Among these, as the structural unit having a preferable acidic group, carboxylic acid, chalcogen analog of carboxylic acid, carbohydrazone acid [RC (═NNH ₂ ) OH], carboxymidic acid [RC (═NH) OH], Sulfonic acid [RS (O) ₂ OH], sulfinic acid [RS (O) OH], sulfenic acid [RSOH], selenonic acid [RSe (O) ₂ OH], selenic acid [RSe (O) OH], selenic acid Structural units derived from analogs of [RSeOH], phosphoric acid and its acid-related compounds, silicic acid, and boric acid, particularly preferred are structural units derived from acrylic acid, methacrylic acid, and phosphoric acid.

  (B) The content of the structural unit having an acidic group in the binder resin is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 30 mol% or less. Within this range, the surface smoothness and heat resistance during development are good.

(B) The binder resin may contain other structural units in addition to the structural units described above. Examples of other structural units include structural units derived from the following unsaturated monomers.
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Such as (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Saturated carboxylic acid esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; unsaturated carboxylic acid oxetanyl esters such as oxetanyl (meth) acrylate; vinyl acetate, Carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate and vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane;
These components derived from unsaturated monomers may be used alone or in combination of two or more.

  Below, the exemplary compounds 1-1 to 1-8 and 2-39 of (B) binder resin are shown. (B) Binder resin is not limited to these exemplary compounds.

  (B) As a weight average molecular weight of binder resin, it is preferable that it is the range of 10000-100000, More preferably, it is the range of 10000-50000, More preferably, it is the range of 10000-40000. Within this range, developability and linearity are good.

  The content of the (B) binder resin in the colored photosensitive resin composition of the present invention is preferably in the range of 10% by mass to 50% by mass, and preferably in the range of 15% by mass to 40% with respect to the solid content of the colored photosensitive resin composition. A range of mass% is more preferred.

  The colored photosensitive resin composition of the present invention may contain (B) a resin having a structure other than the binder resin. (B) As a resin having a structure other than the binder resin, it acts as a binder for the colorant, and when producing a color filter, it is preferably used for a developer used in the development processing step, particularly preferably an alkaline developer. In particular, an acrylic copolymer having a carboxyl group is preferable, and an ethylenically unsaturated monomer having one or more carboxyl groups and other monomers are not particularly limited. A copolymer with a copolymerizable ethylenically unsaturated monomer is preferred.

In the present invention, (B) as a specific example of a resin having a structure other than the binder resin,
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
Etc.

Moreover, the resin containing the following epoxy rings and oxetane rings can also be used.
Styrene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / acrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl acrylate copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) oxetane / t-butyl methacrylate copolymer,
Benzyl methacrylate / methacrylic acid / 3- (methacryloyloxymethyl) -3-ethyloxetane / styrene copolymer,

Butadiene / styrene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Butadiene / methacrylic acid / tricyclomethacrylate methacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / methacrylic acid / tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid-6,7-epoxyheptyl copolymer,
Styrene / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,
t-butyl methacrylate / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl copolymer,
Styrene / methacrylic acid / methyl methacrylate / glycidyl methacrylate copolymer,
p-methoxystyrene / methacrylic acid / cyclohexyl acrylate / glycidyl methacrylate copolymer.

<(C) Polymerizable compound>
The colored photosensitive resin composition of the present invention contains (C) at least one polymerizable compound, and (C) at least one polymerizable compound is a carboxyl group-containing polyfunctional monomer.

[Carboxyl group-containing polyfunctional monomer]
The carboxyl group-containing polyfunctional monomer that can be used in the present invention has at least one carboxyl group in the molecule, preferably 1 to 4, more preferably 1 to 3 carboxyl groups. The monomer which has. Moreover, it has 2 or more of polymerizable unsaturated double bonds as polyfunctionality, Preferably it has 2-12, More preferably, it has 3-6.

Specifically, for example, a free carboxyl group-containing polyfunctional esterified product of a polyhydric alcohol having a valence of 2 or more and a polymerizable unsaturated carboxylic acid having a carboxyl group of 2 or more; (c1) a valence of 3 or more A free carboxyl group-containing esterified product of (T1) a free hydroxyl group-containing polyfunctional ester of a polyhydric alcohol and (c2) a polymerizable unsaturated carboxylic acid having one or more carboxyl groups, and (c3) a dicarboxylic acid (Hereinafter referred to as (C1) a polyfunctional monomer); (c4) a polyfunctional carboxylic acid having a trivalent or higher valence and (c5) a polymerizable unsaturated compound having one or more hydroxyl groups containing a free carboxyl group-containing polyfunctional And the like (hereinafter referred to as (C2) polyfunctional monomer).
(C1) + (c2) → (T1) (1-1)
(T1) + (c3) → (C1) (1-2)
(C4) + (c5) → (C2) (2)

  As the carboxyl group-containing polyfunctional monomer in the present invention, (C1) polyfunctional monomer and (C2) polyfunctional monomer are preferable. (C1) In the polyfunctional monomer, examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol.

  Examples of the polymerizable unsaturated carboxylic acid having one or more carboxyl groups include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. And mesaconic acid.

  Examples of the dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, Examples thereof include methyl succinic acid, tetramethyl succinic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.

  (C2) In the polyfunctional monomer, examples of the trivalent or higher polyvalent carboxylic acids include propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid. Acid, aconitic acid, camphoric acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid Examples thereof include acid, trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid.

  Examples of the polymerizable unsaturated compound having one or more hydroxyl groups include (meth) allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. Etc.

  More specifically, examples of the preferred (C1) polyfunctional monomer and (C2) polyfunctional monomer in the present invention are trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, Monoester group-containing monoesters of monohydroxy group-containing oligo (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid and terephthalic acid Tricarboxylic acids such as propane-1,2,3-tricarboxylic acid, butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, and 2-hydroxyethyl Mono, such as (meth) acrylate and 2-hydroxypropyl (meth) acrylate The mud alkoxyalkyl (meth) acrylates, mention may be made of free carboxyl group-containing oligo ester and the like.

  Examples of the carboxyl group-containing polyfunctional monomer include the following M-1 to M-4. From the viewpoint of photocurability and alkali developability, the following monomer M-1 is used. More preferred.

  In the present invention, the carboxyl group-containing polyfunctional monomer has an acid value of 80 mgKOH / g to 200 mgKOH / g from the viewpoint of developability (line backlash, surface smoothness) due to shortening of development time and compatibility. Preferably there is. More preferably, it is 80 mgKOH / g-150 mgKOH / g, More preferably, it is 80 mgKOH / g-120 mgKOH / g. In the present invention, the acid value is determined by the method described in JIS standard (JIS K 0070: 1992).

  In this invention, a carboxyl group-containing polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The carboxyl group-containing polyfunctional monomer in the present invention is widely known in the industrial field, and in the present invention, these can be used without any particular limitation, and commercially available products may be used or those synthesized appropriately. May be used.

In the colored photosensitive resin composition of the present invention, as the polymerizable compound (C), in addition to the carboxyl group-containing polyfunctional monomer, other polyfunctional monomers may be used in combination.
Here, the ratio of the carboxyl group-containing polyfunctional monomer to the total polyfunctional monomer is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, and particularly preferably 50% by mass. % To 100% by mass. By setting it as the said range, formation of a desired pattern becomes easy and developability becomes favorable.

  Examples of the polyfunctional monomer other than the carboxyl group-containing polyfunctional monomer that can be used in the present invention include monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and their The thing with chemical forms, such as a copolymer, is mentioned. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen atom or the like In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(In the general formula (V), R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  The other polyfunctional monomers described above can be used in combination of two or more, in addition to being used alone.

About these polyfunctional monomers, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a colored photosensitive resin composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, with respect to compatibility and dispersibility with other components contained in the curable composition (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) The selection and use method of the monomer is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

  As the polymerizable compound (C) of the present invention, a monofunctional monomer can be used in combination. The content of the monofunctional monomer is preferably 5 to 90 parts by weight with respect to 100 parts by weight of the polyfunctional monomer (carboxyl group-containing polyfunctional monomer + other polyfunctional monomer). 10-50 weight part is more preferable.

  In the colored photosensitive resin composition of the present invention, the total content of the polymerizable compound (C), ie, “content of carboxyl group-containing polyfunctional monomer + content of other polyfunctional monomer + simple The "functional monomer content" is usually 5 to 500 parts by mass, preferably 20 to 300 parts by mass, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the binder resin. By setting it as the said range, pixel intensity | strength, surface smoothness, and developability become favorable.

  In the colored photosensitive resin composition of the present invention, the total content of the polymerizable compound (C) is preferably 5% by mass to 40% by mass in the total solid content of the colored photosensitive resin composition, and 15% by mass. It is more preferable that it is% -40 mass%, and it is still more preferable that it is 20 mass%-40 mass%.

  In the colored photosensitive resin composition of the present invention, the mass ratio ((D) photopolymerization initiator / (C) polymerizable compound) between (C) the polymerizable compound and (D) the photopolymerization initiator described later is 0.00. 1 or more and 2.0 or less, preferably 0.1 or more and 1.0 or less, particularly preferably 0.3 or more and 0.9 or less. By setting it within the above range, the pattern formability is good and the adhesion to the substrate is excellent. Further, the amount of mask thickening after exposure and development is sufficient, and pattern peeling is suppressed.

<(D) Photopolymerization initiator>
The colored photosensitive resin composition of the present invention contains (D) at least one photopolymerization initiator, and (D) at least one photopolymerization initiator is a lophine photopolymerization initiator or an oxime photopolymerization initiator. It is an agent.

  (D) As a lophine type photoinitiator used as a photoinitiator, a hexaaryl biimidazole compound is mentioned, for example. Examples of the hexaarylbiimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) ) Biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4- Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichloro) Phenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5 ′ -Tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2' -Bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5 5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxyca Bonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethyl) Phenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4 -Ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2 -Phenylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-phenylphenyl) -4,4', 5,5'-tetrakis (4-phenoxy) Carbonylphenyl) biimidazole,

2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (4-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (3-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole ,

2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) ) -4,4 ', 5,5'-tetraphenylbiimi Sol, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4', 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2-fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Among these, particularly preferable compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, B-CIM, manufactured by Hodogaya Chemical Co., Ltd.), 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (for example, HABI1311 manufactured by Nippon Siebel Hegner), 2,2′-bis (2 -Methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, black gold chemical).
These may be used alone or in combination of two or more.

  (D) As an oxime system photoinitiator used as a photoinitiator, an oxime ester compound, a ketoxime compound, etc. are mentioned, for example. Among these, from the viewpoint of sensitivity and coloring after baking, a ketoxime photopolymerization initiator represented by the following general formula (III) is preferable.

  In general formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of X are present, the plurality of X each independently represents a monovalent substituent.

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. Good phosphinoyl group, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, dialkyl which may have a substituent Aminocal Group, optionally dialkylaminothiocarbonyl group, or the like may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, taran Rasenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. It is done.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  As the aryloxycarbonyl group which may have a substituent, phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

  Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

R is more preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, specifically, an unsubstituted or substituted acetyl group, propionyl group, benzoyl group, toluyl group. Is preferred.
Examples of the substituent include groups represented by the following structural formula, and among these, any of (d-1), (d-4), and (d-5) is preferable.

Examples of the divalent organic group represented by A include alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent. Is mentioned.
Examples of the substituent that can be introduced into these groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group, methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, Alkylamino groups such as cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert- In addition to alkyl groups such as butyl group and dodecyl group, phenyl groups, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group Group, triphenylphenacylphos Honiumiru group, and the like.

  Among them, the A is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. An alkylene group, an alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl) An alkylene group substituted with a group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, Ar is phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2- Azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl Group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group , Quarter anthracenyl group, anthraquinolyl group, phena Tolyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group , A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy such as methoxy group, ethoxy group and tert-butoxy group. Aryloxy groups such as phenoxy groups, p-tolyloxy groups, alkylthiooxy groups such as methylthiooxy groups, ethylthiooxy groups, tert-butylthiooxy groups, phenylthiooxy groups, p-tolylthiooxy groups, etc. Alkoxycarbonyl groups such as ruthiooxy group, methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Methoxalyl group An alkylsulfanyl group such as an acyl group, a methylsulfanyl group, and a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group, an alkylamino group such as a methylamino group and a cyclohexylamino group, and a dimethylamino group Dialkylamino groups such as diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group, carboxy group, Formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammo Umiru group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  In the general formula (III), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

  Examples of the monovalent substituent represented by X include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, and a substituent. A good arylthiooxy group, a halogenated alkyl group that may have a substituent, an amide group that may have a substituent on N, an acyloxy group that may have a substituent, and a substituent May have an alkylsulfanyl group, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, or a substituent. Alkylsulfonyl group, substituent An arylsulfonyl group that may have a substituent, an acyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, a carbamoyl group that may have a substituent, and a substituent. Examples thereof include a sulfamoyl group, an amino group which may have a substituent, a phosphinoyl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-ni Rofenashiru group, and the like.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, taran Rasenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. Tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarb Methylpropenylmethyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  The alkylthiooxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group Group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethylhexyl Examples include a thiooxy group, a decylthiooxy group, a dodecylthiooxy group, an octadecylthiooxy group, and a benzylthiooxy group.

  The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenyl There is thiooxyacids group, and the like.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl Carbamoyl group N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like can be mentioned.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.

  Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthiooxy group that may have a substituent, an arylthiooxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. A good arylsulfinyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbo which may have a substituent D Groups, carbamoyl groups which may have substituents, sulfamoyl groups which may have substituents, amino groups which may have substituents, heterocyclic groups which may have substituents, It may be substituted with a substituent.

  Examples of such a substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Aryloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Acyl groups such as methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino group such as amino group, Dimethylamino group such as dimethylamino group, Diethylamino group, Morpholino group, Piperidino group, Arylamino group such as phenylamino group, p-tolylamino group, Methyl group, Ethyl group, Tert-butyl group In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl Etc. The.

  Among these, X has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy which may have a substituent A group, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or a substituent on N A good amide group is preferable, and an alkyl group which may have a substituent is more preferable.

Moreover, although n in general formula (III) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In the general formula (III), when a plurality of Xs are present, the plurality of Xs may be the same or different.

  Specific examples of the photopolymerization initiator represented by the general formula (III) are shown below.

  The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  In the colored photosensitive resin composition of the present invention, as a photopolymerization initiator (D), a photopolymerization initiator other than a lophine photopolymerization initiator and an oxime photopolymerization initiator may be used in combination. As the photopolymerization initiator other than the lophine photopolymerization initiator and the oxime photopolymerization initiator, any known compound can be used without limitation as long as it is a compound that initiates and accelerates the polymerization of the polymerizable compound (C). Can do. Specifically, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid compounds, Examples thereof include disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples thereof include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), U.S. Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Patent Laid-Open No. 48-. JP 36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.K. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, Japanese Patent Publication No. 6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622, 286, etc., JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech'98. Proceeding April 19-22. , 1998, Chicago ”etc. Urate, JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554, JP-A-6-175553, JP-A-9-188710 JP, 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-292014, J. Pat. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 A, JP 2000-80068 A, JP 2004-534797 A, etc. Specific examples are the photopolymerization initiators described.

  (D) When using a photopolymerization initiator having no absorption at the exposure wavelength as the photopolymerization initiator, it is preferable to use a compound having absorption at the exposure wavelength as the sensitizer. The sensitizer will be described later.

  The content of the photopolymerization initiator (D) used in the present invention is preferably in the range of 5% by mass to 20% by mass with respect to the total solid content of the colored photosensitive resin composition, and in the range of 5% by mass to 15% by mass. Is more preferable, and the range of 10% by mass to 15% by mass is still more preferable.

  In the colored photosensitive resin composition of the present invention, (B) the binder resin has at least the (B-1) in the molecule, and (C) the polymerizable compound (C1) is a polyfunctional monofunctional monomer. A ketoxime system represented by the general formula (III) as a photopolymerization initiator, comprising at least one of a monomer, the (C2) polyfunctional monomer, and the monomer M-1. The aspect which contains a photoinitiator is preferable.

<(E) Solvent>
The colored photosensitive resin composition of the present invention contains (E) a solvent and can be prepared using the (E) solvent. The pigment dispersion composition described above is also prepared using the solvent (E).
(E) Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate), 2-oxypropionic acid 2-oxypropionic acid alkyl esters such as til, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, and 2-ethoxy -2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate etc;

Ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol mono n-propyl ether , Propylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene glycol phenyl ether,
Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diacetate, Propylene glycol n-butyl ether acetate, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tripropylene glycol methyl Chromatography ether acetate and the like;

  Alkoxyalkyl acetates such as 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 2 -Ethoxybutyl acetate, 4-ethoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3 -Methyl-4-methoxypentyl acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol and the like;
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like are preferable.
(E) A solvent may be used in combination of two or more, in addition to being used alone.

  The colored photosensitive resin composition of the present invention may further contain other components such as (F) a sensitizer, a surfactant, and a thermosetting resin, if necessary.

<(F) Sensitizer>
In the colored photosensitive resin composition of the present invention, it is preferable to use a compound having absorption at the exposure wavelength as a sensitizer to increase the initiation efficiency of the (D) photopolymerization initiator.
By exposure at a wavelength that can be absorbed by the sensitizer, the radical generation reaction of the (D) photopolymerization initiator component and the polymerization reaction of the polymerizable compound thereby are accelerated.
Examples of such a sensitizer include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Spectral sensitizing dyes or dyes preferred as sensitizers that can be used in the present invention include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose bengal), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, Chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyllin) Chlorophyllin, central metal-substituted chlorophyll), metal complexes, anthraquinones (for example, anthraquinone), squaliums (for example, squalium), carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds , Coumarin compounds, azide compounds, metallocene compounds, organic boric acid compounds, disulfonic acid compounds and the like, and ethylaminobenzophenone, thioxanthone and thiol compounds are preferred.

The thiol compound often has no absorption at the exposure wavelength, but acts as a chain transfer agent to further improve the sensitivity of the initiator to actinic radiation, or to suppress the inhibition of polymerization of the polymerizable compound by oxygen. Have.
Examples of the thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (PETP), and the like. Single functional groups such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, N-phenyl-mercaptobenzimidazole, etc. A functional thiol compound is mentioned.
In particular, a monofunctional thiol compound is preferable from the viewpoint of stability over time and solubility in a solvent.

  The content of the thiol compound in the colored photosensitive resin composition of the present invention is 0. 0% relative to the total solid mass of the photosensitive resin composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. The range of 5-10 mass% is preferable, and the range of 0.5-5 mass% is more preferable.

(Surfactant)
The colored photosensitive resin composition of the present invention can contain a surfactant.
Since the thixotropy of the coating liquid generally increases when the pigment concentration is increased, the film after the colored photosensitive resin composition layer (colored layer coating film) is formed by applying or transferring the colored photosensitive resin composition onto the substrate Thickness unevenness is likely to occur. In particular, in the formation of a colored photosensitive resin composition layer (colored layer coating film) by the slit coating method, the coating liquid for forming the colored photosensitive resin composition layer is leveled before drying to form a uniform thickness coating film. It is important to. For this reason, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above, manufactured by ADEKA Corporation), Emulgen series, Rheodor series (above, produced by Kao Corporation), Eleminor series, Nonipole Series, Octapole Series, Dodecapol Series, New Pole Series (Sanyo Chemicals Co., Ltd.), Pionein Series (Takemoto Yushi Co., Ltd.), Nissan Nonion Series (Nippon Yushi Co., Ltd.), etc. It is. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, F780, F781, F782, F784, F552, F554, R554, R30, and R08. (Above, manufactured by DIC Corporation), FLORARD FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( As mentioned above, Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (above, manufactured by JEMCO).

Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).
Among these, the preferred surfactants for the present invention are Megafac F780, F781, F782, F784, F552, and F554 (manufactured by DIC Corporation).

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, and still more preferably 0.5 parts by mass or less with respect to 100 parts by mass of the colored photosensitive resin composition. When the amount of the surfactant exceeds 5 parts by mass, streaks and surface roughness are likely to occur during coating and drying, and smoothness tends to deteriorate.

(Thermosetting resin)
The colored photosensitive resin composition of the present invention can contain a thermosetting resin such as an epoxy resin or an oxetane resin, if desired.
Examples of the epoxy resin include bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compounds.

For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. , Manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. These similar bisphenol F type and bisphenol S type can also be mentioned. Ebecryl
Epoxy acrylates such as 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  The cresol novolak type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl type 3,5,3 ', 5'-tetramethyl-4,4'diglycidylbiphenyl and the like.

  Examples of the alicyclic epoxy compound include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 and the like (above, manufactured by Tohto Kasei) and the like can be mentioned. In addition, Epototo YH-434 and YH-434L, which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can be used.

  Among these epoxy resins, preferably novolak type epoxy compounds and alicyclic epoxy compounds are preferable, and those having an epoxy equivalent of 180 to 250 are particularly preferable. Examples of such a material include Epicron N-660, N-670, N-680, N-690, YDCN-704L (manufactured by DIC Corporation), and EHPE3150 (manufactured by Daicel Chemical Industries).

As the oxetane resin, Aron oxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
The oxetane resin can be used alone or mixed with an acrylic copolymer, an epoxy resin and a maleimide resin. In particular, when used in combination with an epoxy resin, the reactivity due to heat generated by ultraviolet laser exposure is high, which is preferable from the viewpoint of adhesion to the substrate.
As content in the colored photosensitive resin composition of the epoxy resin which concerns on this invention, and an oxetane resin, 0.5-15 mass% is preferable with respect to the total solid of a colored photosensitive resin composition, 1- 10% by mass is preferable from the viewpoint of both solubility in alkali and adhesion to the substrate.

(Organic carboxylic acid)
In order to promote the alkali solubility of the uncured part and further improve the developability of the colored photosensitive resin composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. Can do. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Phenoxyacetic acid, methoxyphenoxy acetic, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

(Silane coupling agent)
A silane coupling agent can be used for the colored photosensitive resin composition of this invention from a viewpoint of the adhesive improvement with the further board | substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material. In addition, it preferably has a group that interacts or forms a bond with an organic resin and exhibits an affinity, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group. Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.
That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and specifically, a (meth) acryloyl-tri having the following structure. Examples include methoxysilane compounds and glycidyl-trimethoxysilane compounds.

  As the addition amount in the case of using a silane coupling agent, the total solid content in the colored photosensitive resin composition used in the present invention is preferably in the range of 0.2% by mass to 5.0% by mass, 0.5 mass%-3.0 mass% are more preferable.

(Polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored photosensitive resin composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

The addition amount of the thermal polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the colored photosensitive resin composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to prevent polymerization inhibition due to oxygen and can be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The addition amount of the higher fatty acid derivative is preferably 0.5% by mass to 10% by mass of the colored photosensitive resin composition.

(Plasticizer)
Furthermore, in the present invention, an inorganic filler, a plasticizer, or the like may be added in order to improve the physical properties of the colored photosensitive resin composition.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like (C) polymerizable compound ( B) 10 mass% or less can be added with respect to the total mass with binder resin.

  Although the colored photosensitive resin composition of the present invention can be cured by a conventionally known exposure means, among them, it is cured with high sensitivity by exposure to ultraviolet light and exhibits high adhesion to a substrate. The ultraviolet light exposure means may be either a laser exposure method or a proximity exposure method, but a laser exposure method is preferred from the viewpoint of suppressing surface reticulation. The colored photosensitive resin composition of the present invention can be preferably used for forming a colored pattern of a color filter.

≪Pattern forming method, color filter and manufacturing method thereof≫
The colored photosensitive resin composition and the pattern forming method of the present invention are suitable for a color filter for a liquid crystal display device. Hereinafter, a pattern forming method using the colored photosensitive resin composition of the present invention will be described as a pattern forming method in a method for producing a color filter for a liquid crystal display device, but the present invention is not limited to this method. .

  The pattern forming method of the present invention includes a colored layer forming step of forming a colored layer by applying the colored photosensitive resin composition of the present invention on a substrate, and exposing the colored layer with a pattern-like ultraviolet laser. And an exposure step for forming a latent image, and a development step for developing a colored layer on which the latent image is formed to form a pattern. Furthermore, you may provide the process (baking process) of baking the said colored layer and the process (baking process) of baking the developed said colored layer as needed. These processes may be collectively referred to as a pattern formation process.

[Colored layer forming step]
In the colored layer forming step in the present invention, the colored photosensitive resin composition of the present invention is applied on a substrate to form a colored layer. As the substrate, for example, non-alkali glass, soda glass, borosilicate glass, quartz glass used for liquid crystal display devices and the like, and a substrate obtained by attaching a transparent conductive film thereto, a photoelectric conversion element substrate used for a solid-state imaging device, etc. Is mentioned. Furthermore, a plastic substrate can also be used. It is preferable that a black matrix is formed in a lattice shape or the like using these substrates, and a colored pattern is formed in an empty portion of the lattice.

  If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) from the standpoint of achieving the effects of the present invention.

As a method for forming the colored layer on the substrate, various application methods such as slit coating, ink-jet method, spin coating, cast coating, roll coating, and screen printing can be applied. Of these, slit coating is preferred from the viewpoints of accuracy and speed.
Moreover, the method of transferring on the board | substrate the coating film previously provided and formed by the said application | coating method on the temporary support body can also be applied.
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.

  The thickness of the colored layer in the present invention (for example, coating thickness) is 0.5 μm to 3.0 μm after drying to obtain a sufficient color reproduction region and sufficient panel luminance. It is preferable to form so that it may become, and it is more preferable to set it as 1.5 micrometers-2.5 micrometers.

[Exposure process]
In the exposure step in the present invention, the colored layer is exposed to a pattern-like ultraviolet laser to form a latent image. By the exposure process of the present invention, (C) the polymerization curing reaction of the polymerizable compound occurs and proceeds due to the initiation species generated from the (D) photopolymerization initiator in the patterned exposure region in the colored photosensitive resin composition. At the same time, the allyl group, N-substituted maleimide group, or cyclic imide group present in the molecule of the binder resin (B) due to heat generated by ultraviolet laser exposure causes a thermal reaction, and a curing reaction occurs and proceeds. It is considered that a pattern composed of a cured region and an uncured region is formed by the light and heat dual curing of the exposed region.

  Laser excitation media include crystals, glass, liquids, dyes, gases, etc., and lasers having oscillation wavelengths for known ultraviolet light, such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers, are used from these media. Can do. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  The exposure wavelength of the ultraviolet laser used in the present invention is preferably in the range of 300 nm to 380 nm, more preferably in the range of 310 nm to 360 nm, particularly 355 nm, in terms of good sensitivity that matches the photosensitive wavelength of the colored photosensitive resin composition. A wavelength laser exposure method is preferred.

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
As the exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  The ultraviolet laser used in the present invention is preferably a pulse laser oscillated at a frequency of 20 Hz to 2000 Hz from the viewpoint of productivity.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available ones such as EGIS (buoy technology) or DF2200G (Dainippon Screen Co., Ltd.) can be used. These devices are also preferably used.

  The ultraviolet laser has good light parallelism, and pattern exposure can be performed without using a mask during exposure, but the pattern shape is affected by the shape and profile of the output light. Therefore, it is preferable to expose the pattern using a mask because the linearity of the pattern becomes high.

[Development process]
In the developing step in the present invention, the colored layer on which the latent image is formed is developed to form a pattern. The exposure area by the ultraviolet laser is cured in a pattern, and in the development process, the unexposed part (uncured part) in the exposure process is removed by elution in an alkaline aqueous solution by performing an alkali development process. The pattern can be formed by leaving only the photocured part.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the concentration of these alkaline compounds is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

The development temperature is preferably 20 ° C to 35 ° C, more preferably 23 ° C to 30 ° C. The development time is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, it is possible to arbitrarily design the pattern shape to be rectangular or forward tapered.

[Bake process]
In the present invention, in order to complete the curing of the colored photosensitive resin composition, it is preferable to provide a baking step for baking the developed colored layer. Baking is performed by heating a substrate having a pattern after development and rinsing in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like. It can be carried out.
As conditions for baking, the temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 20 minutes to 90 minutes.

  When forming a colored pattern of a plurality of hues such as RGB three hues and a light shielding layer, the cycle of forming the colored layers, exposing, developing, and baking may be repeated for the desired number of hues. After the colored layer is formed, exposed, and developed, all the hues may be finally baked. As a result, a color filter including colored pixels having a desired hue is produced.

[Other processes]
In this invention, you may provide the process of prebaking in order to dry the colored layer formed by application | coating etc. before an exposure process. The prebaking temperature of the colored layer is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

≪Liquid crystal display device≫
The color filter of the present invention is suitable for the production of a liquid crystal display device, and the liquid crystal display device using the color filter produced by the pattern forming method of the present invention can display a high-quality image.
For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)). The liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Issued in 1994 by Industrial Research Co., Ltd.)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.

The color filter for a liquid crystal display device is particularly effective for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".
In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter for a liquid crystal display element of the present invention can be applied to a liquid crystal display device composed of these known members.
For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi Co., Ltd.) Fuji Chimera Research Institute, published in 2003) ”.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Yukiaki Yagi), etc. Are listed.

  When the color filter produced by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a conventionally known three-wavelength tube of a cold cathode tube, a high contrast can be realized. By using a light source (RGB-LED) as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “%” and “part” are based on mass.

Exemplified compounds 1-1, 1-2, 1-3, 31, 35, and 39 listed in the section of (B) binder resin were synthesized by the following method.
(Synthesis Example 1: Synthesis of Exemplified Compound 1-1)
54 g of 1-methoxy-2-propanol was placed in a 200 mL three-necked flask equipped with a stirring rod provided with stirring blades, a reflux condenser, and a thermometer, and heated to 70 ° C. under a nitrogen stream. A solution prepared by dissolving 10.07 g of allyl methacrylate, 1.93 g of methacrylic acid and 0.185 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 54 g of 1-methoxy-2-propanol It dropped in the three necked flask over 2.5 hours using the jar pump. After completion of dropping, the mixture was further stirred at 70 ° C. for 2 hours. After completion of heating, it was poured into 1 L of water and re-precipitated. The precipitate was filtered and then vacuum-dried to obtain 9 g (yield 75%) of a binder resin.
As a measurement sample of the weight average molecular weight, 0.01 g of the obtained binder resin was weighed into a 10 mL volumetric flask, and about 8 mL of tetrahydrofuran was added and dissolved at room temperature. This solution was measured using gel permeation chromatography (GPC). The weight average molecular weight of exemplary compound 1-1 (allyl methacrylate / methacrylic acid copolymer, molar ratio = 80/20) was 35,000.

  Moreover, according to the synthesis method of the exemplary compound 1-1, exemplary compound 1-2 (allyl methacrylate / methacrylic acid copolymer, molar ratio = 50/50, weight average molecular weight 35000), and exemplary compound 1-3 (Allyl methacrylate / methacrylic acid copolymer, molar ratio = 40/60, weight average molecular weight 35000) was synthesized.

(Synthesis Example 2: Synthesis of Exemplified Compound 31)
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 51.9 parts by mass of N-phenylmaleimide and allyl methacrylate 62. Nitrogen was charged with 3 parts by mass, 16.8 parts by mass of methacrylic acid, and 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) as a molecular weight regulator. Replaced. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 20.0% by mass). The weight average molecular weight of Exemplified Compound 31 measured using GPC was 35000.

(Synthesis Example 3: Synthesis of Exemplified Compound 35)
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 124.6 parts by mass of cyclohexylmaleimide and 25.2 parts of methacrylic acid. 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD manufactured by NOF Corporation) as a molecular weight regulator and a molecular weight regulator were charged, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 20.0% by mass). The weight average molecular weight of Exemplified Compound 35 measured using GPC was 20000.

(Synthesis Example 4: Synthesis of Exemplary Compound 36)
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 111.0 parts by mass of N—CH ₂ -Ph maleimide, 34.4 parts by mass of methacrylic acid and 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) were charged as a molecular weight regulator, and the atmosphere was replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 20.0% by mass). The weight average molecular weight of Exemplified Compound 36 measured using GPC was 18,000.

(Synthesis Example 5: Synthesis of Exemplified Compound 39)
According to the method of Kato et al. (Kato, S., Sato, K., Maeda, D., Nomura, M. Colloids Surfaces A: Physiochem. Eng. Aspects, 1999, 153, 127 (1999)), Then, the exemplified compound 39 was synthesized from the compound and methacrylic acid by the method of Okazaki (Okazaki, E. Proceedings of the Radtech Europe 2001). The weight average molecular weight of the exemplary compound 39 measured using GPC was 20000.

(Preparation of green pigment zinc halide phthalocyanine dispersion)
-Synthesis of zinc halide phthalocyanine pigments-
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride.
Halogenation was performed by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride and 1 part of zinc phthalocyanine at 40 ° C., and dropping 2.2 parts of bromine. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

1 part of this partially brominated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol and 0.09 part of xylene were charged into a double arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a partially brominated zinc phthalocyanine pigment.
The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) and contains an average of 10 bromines in one molecule, based on a halogen content analysis by mass spectrometry. there were.
The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

  In a high-speed disperser “TSC-6H” manufactured by Igarashi Machinery Manufacturing Co., Ltd. charged with zirconia beads having a diameter of 0.5 mm, 14.9 parts of the partially brominated zinc phthalocyanine pigment (referred to as PG58) obtained above, acrylic manufactured by Big Chemie 7.1 parts of a dispersant “BYK-2001” and 78 parts of propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as PGMEA) were charged and stirred at 2000 rpm for 8 hours for partial bromination. A dispersion of a zinc halide phthalocyanine pigment (referred to as green pigment PG58) was prepared.

(Preparation of dispersion of yellow pigment PY150)
-Synthesis of Resin (i-1)-
6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1). A synthesis scheme is shown below.

-Synthesis of Resin (J-1)-
10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) and 100 g of the polyester resin (i-1) are mixed and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). Obtained. Then, it stood to cool to 65 degreeC, PGMEA200g containing 3.8g of succinic anhydrides was added slowly, and it stirred for 2 hours. Thereafter, PGMEA was added to obtain a 10 mass% PGMEA solution of the resin (J-1). The resin (J-1) has a side chain derived from the polyester resin (i-1) and a carboxy group derived from succinic anhydride. A synthesis scheme is shown below.

  As a pigment, C.I. I. 15 parts (average particle diameter 60 nm) of Pigment Yellow 150 (PY150), 7.5 parts of the resin (J-1), and 77.5 parts of PGMEA were mixed and dispersed by a bead mill (zirconia beads 0.3 mm) for 3 hours. A dispersion of yellow pigment PY150 was prepared.

[Example 1]
(Preparation of colored photosensitive resin composition)
Pigment dispersion 1 was prepared as follows. That is, with the composition described below, a homogenizer was used and stirred for 3 hours at a rotation speed of 3,000 rpm to prepare a mixed solution, and further bead dispersion using 0.1 mmφ zirconia beads Dispersion treatment was carried out for 8 hours using a machine Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.)

・ C. I. Pigment Blue 15: 6 11.8 parts C.I. I. Pigment Violet 23 1.0 part Disperbyk 161 (manufactured by Big Chemie, 30% solution) 24.0 parts PGMEA 63.2 parts

  Components of the following composition were further added to the obtained pigment dispersion 1, and mixed by stirring to prepare a colored photosensitive resin composition for blue phase (B).

Pigment dispersion 1 39.20 parts Binder resin: 20% PGMEA solution of Exemplified Compound 1-1 16.40 parts Polymerizable compound: M-510 (carboxyl group-containing polyfunctional monomer) 4.57 parts (Toagosei Co., Ltd., Aronix M-510, acid value 100 mgKOH / g)
Photopolymerization initiator: Compound A (the following structure) 2.74 parts Sensitizer: Monofunctional thiol compound SH-1 (the following structure) 0.55 parts Epoxy compound: EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.) 0 .60 parts Solvent: PGMEA and 3-ethoxyethyl propionate (= 80/20 [mass ratio]) mixed solution 35.51 parts Polymerization inhibitor: p-methoxyphenol 0.01 part Adhesion modifier : KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.40 parts ・ Surfactant: Megafac F-780 (manufactured by DIC Corporation) 0.02 parts

(Pattern formation)
The pattern was formed by performing the following steps unless otherwise specified.
The colored photosensitive resin composition obtained above was applied onto the surface of a non-alkali glass substrate (Corning, 1737, 550 mm × 660 mm) using a slit coater (Hirata Kiko Co., Ltd., HC-6000). After that, pre-baking was performed for 120 seconds in a clean oven at 90 ° C. to form a colored layer having a thickness of 2.0 μm.
Next, using EGIS (Bui Technology Co., Ltd., third harmonic of YAG laser (355 nm), pulse width 6 ns) as a laser exposure apparatus, a colored layer on the substrate is passed through a photomask having a line and space of 20 microns width. The gap (gap) between the surface of the substrate and the photomask was 200 μm, and pulse irradiation (frequency 50 Hz) of about 1 mJ / cm ² was performed 20 times (exposure amount 20 mJ / cm ² ).
Then, using this developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer (CDK-1) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) is used. The shower pressure was set at 0.20 MPa with 1 part by mass, 99 parts by mass of pure water diluted at 25 ° C.), developed for 50 seconds, washed with pure water, and then air-dried. Then, it baked for 30 minutes in a 220 degreeC clean oven, and formed the blue line pattern on the board | substrate.

The following evaluation was performed on the formed line pattern. The results are shown in Table 2.
(Evaluation of line width sensitivity)
The formed line pattern was observed with an optical microscope (200 times), and the line width was measured and evaluated.

-Evaluation criteria-
A: 30 μm or more B: 27 μm or more and less than 30 μm C: 25 μm or more and less than 27 μm D: Less than 25 μm E: The pattern is not formed or cannot be evaluated.

(Evaluation of linearity)
The formed line pattern was observed with an optical microscope (200 times), and the linearity (roughness) of the line width was visually evaluated.

-Evaluation criteria-
A: There was no backlash, no burrs, and the line was straight.
B: There were several backlashes, but the line was almost straight.
C: The backlash was large and the line width was about ± 2 μm.
D: The backlash was large and the line width was about ± 5 μm.
E: The pattern was not formed or peeled off and could not be evaluated.

(Evaluation of heat resistance)
The substrate on which the line pattern was formed was additionally baked in a clean oven at 240 ° C. for 60 minutes, and the color difference (ΔE ^* ab) before and after the additional baking was measured using a spectrophotometer MCPD-2000 manufactured by Otsuka Electronics Co., Ltd. It was measured. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system. Using the value of ΔE ^* ab, the heat resistance was evaluated according to the following evaluation criteria.

-Evaluation criteria-
5: ΔE ^* ab is 0 or more and less than 1.0 4.5: ΔE ^* ab is 1.0 or more and less than 2.0 4: ΔE ^* ab is 2.0 or more and less than 3.0 3.5: ΔE ^* ab is 3.0 or more and less than 3.5 3: ΔE ^* ab is 3.5 or more and less than 4.0 2.5: ΔE ^* ab is 4.0 or more and less than 5.0 2: ΔE ^* ab is 5.0 or more 1: There is peeling and ΔE ^* ab is 5.0 or more

(Evaluation of developability)
The colored photosensitive resin composition was applied onto the surface of the alkali-free glass substrate using a spin coater so that the dry film thickness was 2.0 μm, and pre-baked at 120 ° C. for 2 minutes to form a uniform colored layer. . Next, as described above, pulse irradiation using a laser exposure apparatus was performed.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the colored layer on the substrate, and then a KOH developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji Film). Shown with a flat nozzle pressure of 0.04 MPa at 24 ° C. every 5 seconds and then rinsed with running water for 20 seconds, followed by drying with an air knife and a line pattern. Got.

  In forming the line pattern, the developability was evaluated as follows. That is, the development was extended from 10 seconds to 5 seconds, and the time required for the uncured part to be removed from the substrate was measured.

(Evaluation of reticulation)
In the formation of the pattern, the exposure was performed using a mask having a line and space with a width of 20 microns and a width of 200 microns and a gap (gap) between the surface of the colored layer on the substrate and the mask of 200 μm. The formed line patterns having a line width of 20 microns and 200 microns after post-baking were observed with an optical microscope (200 times), and the reticulation was visually evaluated.

-Evaluation criteria-
A: Both 200 microns and 20 microns were flat without reticulation.
B: There was no reticulation at 200 microns, but reticulation occurred slightly at 20 microns.
C: There was no reticulation at 200 microns, but reticulation was strong at 20 microns.
D: Reticulation occurred slightly at 200 microns, and reticulation occurred strongly at 20 microns.
E: Reticulation was strong in both 200 microns and 20 microns.

(Comprehensive evaluation)
Line width sensitivity, linearity, heat resistance, developability, and reticulation were comprehensively evaluated according to the following evaluation criteria.
-Evaluation criteria-
5: Very good.
4.5: Excellent.
4: Level at which there is no problem in normal use.
3.5: Slightly inferior performance, but no problem level.
3: Level of barely in normal use.
2.5: There is a problem that is slightly lower than the allowable limit of normal use.
2: Not usable due to insufficient performance.
1: Level that cannot be evaluated.

[Examples 2 to 23, Comparative Examples 1 to 6]
In the preparation of the colored photosensitive resin composition of Example 1, each colored photosensitive resin composition was prepared in the same manner as in the preparation of the colored photosensitive resin composition of Example 1, except that each material used was changed as shown in Table 1. A product was prepared. Examples of the colorant for the red phase (R) include C.I. I. Pigment Red 254 was used. Examples of colorants for the green phase (G) include C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150 was used by mixing at a mass ratio of the former to the latter of 70/30.
The line patterns of Examples 2 to 23 and Comparative Examples 1 to 6 were formed in the same manner as the pattern formation in Example 1 using each colored photosensitive resin composition. Evaluation similar to Example 1 was performed using the obtained line pattern. The results are shown in Table 2.

In Examples 15 to 17, proximity exposure was performed instead of laser exposure in pattern formation and evaluation of developability and reticulation. The conditions for proximity exposure are as follows. In other words, with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the substrate and mask (quartz exposure mask having an image pattern) are vertically set on the substrate. The distance between the colored layer surface and the mask was set to 200 μm, and pattern exposure was performed at an exposure amount of 20 mJ / cm ² .

Example 24
(Preparation of colored photosensitive resin composition)
The following components were stirred and mixed to prepare a colored photosensitive resin composition.
-Dispersion of the green pigment PG58 32.68 parts-Dispersion of the yellow pigment PY150 14.56 parts-Binder resin: 0.176 parts of Exemplified Compound 1-1-Polymerizable compound: TO-2349 (multiple carboxyl group-containing compounds) Functional monomer) 5.52 parts (Toagosei Co., Ltd., Aronix TO-2349, acid value 67 mgKOH / g)
・ Lophine-based photopolymerization initiator: HABI-1311 (structure shown below) 1.115 parts (manufactured by Nippon Siebel Hegner)
-Photopolymerization initiator: 1.246 parts IRGACURE OXE-01 (manufactured by Ciba Specialty Chemicals)
Photopolymerization initiator: KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd. 0.036 parts) Sensitizer: Monofunctional thiol compound SH-1 0.161 parts Solvent: 3-ethoxyethyl propionate 24. 60 parts / solvent: propylene glycol monomethyl ether acetate 12.89 parts / polymerization inhibitor: P methoxyphenol 0.003 part / surfactant: Megafax F-554 (manufactured by DIC Corporation) 0.0146 part

(Pattern formation)
The colored photosensitive resin composition obtained above is coated on the surface of a non-alkali glass substrate (Corning, 1737, 550 mm × 660 mm) by a slit die with a coating speed of 100 mm / s, a coating gap of 100 μm, and a coating flow rate of 1.3 ml. After coating under the conditions of / s, vacuum drying was performed at an ultimate pressure of 0.5 Torr in a vacuum drying chamber, followed by drying for 120 seconds in an oven at 80 ° C. (prebaking) to obtain a coating film having a thickness of 2.0 μm. . Thereafter, it is subjected to proxy exposure with an ultrahigh pressure mercury lamp at 20 mJ / cm ² (illuminance 35 mW / cm ² ) Gap 200 μm through a photomask having a line and space of 20 microns width, and the coating film after exposure is subjected to an alkali developer CDK-1. A 1% aqueous solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was sprayed in a shower form for 40 seconds, and pure water was sprayed in a shower form for 60 seconds to wash away the developer. Next, the coating film that had been exposed and developed as described above was heat-treated in an oven at 230 ° C. for 40 minutes (post-baking) to form a line pattern on the glass substrate.

  Then, the same evaluation as Example 1 was performed about the formed line pattern. The results are shown in Table 2.

Example 25
In the preparation of the colored photosensitive resin composition of Example 24, the colored photosensitive resin composition of Example 24 was prepared except that the lophine photopolymerization initiator was changed from HABI-1311 to HABI-1311A (the following structure). In the same manner as above, a colored photosensitive resin composition was prepared. Thereafter, in the same manner as in Example 24, a line pattern was formed and evaluated. The results are shown in Table 2.

Example 26
In the preparation of the colored photosensitive resin composition of Example 24, the polymerizable compound was changed from TO-2349 to M-520 (manufactured by Toagosei Co., Ltd., acid value 30.0 mgKOH / g, carboxyl group-containing polyfunctional monomer). A colored photosensitive resin composition was prepared in the same manner as in the preparation of the colored photosensitive resin composition of Example 24 except that the above was changed. Thereafter, in the same manner as in Example 24, a line pattern was formed and evaluated. The results are shown in Table 2.

  In Table 1, M-510 is Aronix M-510 manufactured by Toagosei Co., Ltd., and M-520 is Aronix M-520 manufactured by Toagosei Co., Ltd. M-1 and M-2 are specific examples M-1 and M-2 mentioned in the section of the carboxyl group-containing polyfunctional monomer. M-5 is a mixture of (n = 2 / n = 3 / n = 4) = 60/30/10 in the compound represented by the following structural formula. M-6 is a mixture of (n = 2 / n = 3 / n = 4) = 85/15/5 in the compound represented by the following structural formula.

In Table 1, DPHA is dipentaerythritol hexaacrylate, and Nippon Kayaku product name DPHA was used.
CGI242 is an oxime photopolymerization initiator (manufactured by Ciba Specialty Chemicals).
"B-CIM" replaced Compound A with lophine photopolymerization initiator B-CIM and sensitizing dye EAB (B-CIM: EAB = 2: 1 [mass ratio]) (both manufactured by Hodogaya Chemical Co., Ltd.). .
“Triazine-based” is a triazine-based photopolymerization initiator, 4- [o-bromo-pN, N-bis (ethoxycarbonyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine. .
Compound B is a compound represented by the following structural formula.

  In Table 1, the comparative compound 1 is a copolymer of benzyl methacrylate and methacrylic acid (copolymerization molar ratio 80/20, weight average molecular weight 35000), and the comparative compound 2 is composed of n-propyl methacrylate and methacrylic acid. It is a copolymer (copolymerization molar ratio 80/20, weight average molecular weight 35000).

  As is clear from Table 2, Examples 1 to 26 using the colored photosensitive resin composition of the present invention have high line width sensitivity, excellent linearity, heat resistance, and developability, and generation of reticulation. Was suppressed.

Claims (10)

At least (A) a colorant, (B) a binder resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent,
The content of the colorant (A) is 15% by mass to 60% by mass with respect to the solid content of the colored photosensitive resin composition,
The (B) binder resin has (B-1) a structural unit represented by the following general formula (I), (B-2) a structural unit having an N-substituted maleimide group, and (B-3) in the molecule. ) Having at least one structural unit selected from the group consisting of structural units represented by the following general formula (II), and a structural unit having an acidic group,
At least one of the polymerizable compound (C) is a carboxyl group-containing polyfunctional monomer;
(D) A colored photosensitive resin composition in which at least one of the photopolymerization initiators is a lophine photopolymerization initiator or an oxime photopolymerization initiator.


In the general formula ^(I), the R 11 ^{to R 15} each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl ^{group, R 16} represents a hydrogen atom or a methyl group.


In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkylene group having 1 to 6 carbon atoms. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. R ²³ and R ²⁴ may be bonded to each other to form a carbocycle. The colored photosensitive resin composition according to claim 1, wherein the oxime photopolymerization initiator is a ketoxime photopolymerization initiator represented by the following general formula (III).


In general formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of Xs are present, the plurality of Xs each independently represent a monovalent substituent and may be the same or different.   The colored photosensitive resin composition according to claim 1 or 2, wherein an acid value of the carboxyl group-containing polyfunctional monomer is 80 mgKOH / g to 200 mgKOH / g.   The colored photosensitive resin composition according to any one of claims 1 to 3, further comprising (F) a sensitizer, wherein at least one of the (F) sensitizers is a monofunctional thiol compound. .   A colored layer forming step of forming a colored layer by applying the colored photosensitive resin composition according to any one of claims 1 to 4 on a substrate, and pattern-like ultraviolet light with respect to the colored layer A pattern forming method comprising: an exposure step of exposing with a laser to form a latent image; and a developing step of developing the colored layer on which the latent image is formed to form a pattern.   The pattern forming method according to claim 5, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.   The pattern forming method according to claim 5, wherein the ultraviolet laser is a pulse laser oscillated at a frequency of 20 Hz to 2000 Hz.   A color filter manufacturing method comprising a step of forming a pattern on a substrate by the pattern forming method according to claim 5.   A color filter manufactured by the manufacturing method according to claim 8.   A display device comprising the color filter according to claim 9.